CN108780074A - Chromatographic data processing method and chromatography data system - Google Patents
Chromatographic data processing method and chromatography data system Download PDFInfo
- Publication number
- CN108780074A CN108780074A CN201680083134.1A CN201680083134A CN108780074A CN 108780074 A CN108780074 A CN 108780074A CN 201680083134 A CN201680083134 A CN 201680083134A CN 108780074 A CN108780074 A CN 108780074A
- Authority
- CN
- China
- Prior art keywords
- baseline
- chromatography
- spectrum
- peak
- vector
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/86—Signal analysis
- G01N30/8624—Detection of slopes or peaks; baseline correction
- G01N30/8631—Peaks
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/86—Signal analysis
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/86—Signal analysis
- G01N30/8603—Signal analysis with integration or differentiation
- G01N30/8613—Dividing or multiplying by a constant
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/86—Signal analysis
- G01N30/8603—Signal analysis with integration or differentiation
- G01N30/8617—Filtering, e.g. Fourier filtering
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/86—Signal analysis
- G01N30/8624—Detection of slopes or peaks; baseline correction
- G01N30/8641—Baseline
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/86—Signal analysis
- G01N30/8603—Signal analysis with integration or differentiation
- G01N2030/862—Other mathematical operations for data preprocessing
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- General Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Pathology (AREA)
- Immunology (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Pure & Applied Mathematics (AREA)
- Algebra (AREA)
- Mathematical Optimization (AREA)
- Mathematical Analysis (AREA)
- Mathematical Physics (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
Abstract
The wave spectrum for extracting each peak detected on based on the process object i.e. chromatography of observation data, is made the normalized spectrum set of its intensity value { Sn'} (S10, S11).Then, one of wave spectrum is selected, and in a manner of orthogonal with the vector direction of the spectrum, the vector of the wave spectrum in each time of measuring point based on observation data is projected (S12~S14).In addition, the vector to each wave spectrum in set { Sn ' } similarly projects (S15).The spectrum selected as a result, disappears from set { Sn ' }.Then, the processing for repeating S12~S16 adds up to obtained signal (S17) until the interior spectrum disappearance of set { Sn ' }.Signal after total becomes to indicate the signal of the waveform shape of unknown baseline, therefore the spectrum that baseline is found out by the way that the chromatography of itself and each wavelength obtained from observation data to be fitted, the background signal of each wavelength is calculated according to the baseline spectrum and baseline chromatography.It is not necessarily to the setting etc. that user carries out parameter as a result, baseline can be estimated automatically.
Description
Technical field
The present invention relates to the processing of the chromatographic data processing method and chromatographic data that are handled three-dimensional chromatographic data to fill
It sets, more specifically, is related to the baseline for estimating chromatography or obtains the chromatographic data from the peak chromatography after chromatography removal baseline
Processing method and device, the three-dimensional chromatographic data is by by the multichannel of photodiode array (PDA) detector etc.
Type detector or mass spectrograph be used as the liquid chromatograph (LC) of detector or gas chromatograph (GC) is collected, in addition to time, letter
Other parameters other than number intensity also with wavelength or mass-to-charge ratio etc..
Background technology
In the LC of multi-channel type detector for having used PDA detectors etc., when by the injection for injecting sample to mobile phase
Between put as basic point, repeat to obtain the absorption spectrum within the scope of provision wavelengths relative to the test liquid that elutes from column outlet,
Thus, it is possible to obtain having the three-dimensional chromatographic data of time, wavelength and absorbance (signal strength) these three dimensions.In addition,
In liquid chromatography mass instrument (LC-MS) or gas chromatography mass spectrometer (GC-MS), by repeating defined matter in a mass spectrometer
Lotus can obtain than the scanning survey in range with time, mass-to-charge ratio and signal strength (ionic strength) these three dimensions
Three-dimensional chromatographic data.
Fig. 2 (a) is by the concept map of the obtained three-dimensional chromatographic datas of above-mentioned LC.By being carried from such three-dimensional chromatographic data
It takes in specific wavelength (for example, wavelength X0) time orientation on absorbance data, can make as shown in Fig. 2 (b) at this
Wavelength X0In chromatography (hereinafter referred to as " wavelength chromatography ").In addition, by being extracted from three-dimensional chromatographic data in specific measure
The absorbance data in the wavelength direction of (such as moment tp) is carved, the absorption spectrum of moment tp can be made.
In the case where the known compound for being included to sample based on such chromatographic data quantifies, lead to
Often, the wavelength chromatography for the absorbing wavelength that the target compound maximally shows the absorption of light is made.Then, in the wavelength chromatography
On find out the peak from target compound, calculate the area value at the peak, and with found out in advance the standard curve of its area value into
Row control, calculates quantitative values.Therefore, accurately quantitative in order to carry out, it is important that precisely to be found out in chromatography and mesh
Mark the area value at the corresponding peak of compound.
However, in general, there is the baseline from mobile phase etc. in wavelength chromatography.In addition, there is also from targeted
Close the case where peak of object is with overlap of peaks from other compounds.Therefore, corresponding with target compound in order to accurately find out
Peak area value, need accurately to estimate the baseline from mobile phase etc. and find out eliminating the influence of the baseline, really
Peak region.
For the general data processing equipment of LC systems, has based on the chromatography waveform obtained by measurement and automatically push away
Determine the spike shape processing function of baseline.However, in automatic waveform processing, can not be estimated suitable according to the shape of chromatography waveform
When baseline the case where it is also more.Therefore, as disclosed in Non-patent document 1, in previous data processing equipment, use
By suitably changing or setting the parameter of waveform processing or the algorithm of applicable waveform processing manually, thus, it is possible to estimate more at family
Baseline appropriate.
Fig. 8 is the waveform processing for indicating to record based on non-patent literature 1, according to the baseline and peak P of the presumption of chromatography waveform
Area value computing object region (in figure with oblique line shown in region) an example figure.In fig. 8, (a) be removal negative peak it
It is (b) that will be connected and made with straight line between the bottom at each peak afterwards using signal zero level as baseline by the example of peak vertical segmentation
For the example of baseline, (c) be will be used between the bottom at each peak curve connect and as the example of baseline.It can according to these examples
Know, peak area value differs widely because of the method for drafting of baseline.
Like this, such as in user judge that the baseline drawn by executing the waveform processing of certain algorithm is unsuitable
In the case of, by selecting the waveform processing of other algorithms, more appropriate baseline is found out, so as to improve the essence of peak area value
Degree.However, in this case, user (such as being responsible for the operator of analysis) must voluntarily judge the following contents：Be with straight line also
It is the bottom that curve connects adjacent peak, or in the case where the edge at peak seems longer and extends, will will be partly to which
Only regard the edge at the peak from target compound as.In order to accurately carry out such judgement, operator needs to spike shape
Processing has a degree of experience or technology.Moreover, it is judged that may be because of responsible operator is different different, result
It is, even if original chromatography is identical, it is also possible to be generated in the shape for the peak chromatography waveform for eliminating baseline or peak area value inclined
Difference.
Additionally, there are the waveform shapes that the baseline of the wavelength chromatography in each wavelength influences absorption spectrum.Therefore, based on
In the case that peak appears in the position (i.e. absorbing wavelength) in absorption spectrum and identifies compound, need according to mutually not
Wavelength chromatography in co-wavelength and suitably estimate baseline.However, due to the quantity of the wavelength chromatography obtained by one-shot measurement
It is huge, so it is practically impossible to manually singly carry out the setting of parameter etc. to them and execute at baseline presumption
Reason.
Existing technical literature
Non-patent literature
Non-patent literature 1：《Peak waveform processing is confirmed》, [online], Shimadzu Scisakusho Ltd, 2015
November 13 was retrieved, network address<URL：http://www.an.shimadzu.co.jp/hplc/support/lib/lctalk/
23/23lab.htm>
Invention content
Technical problems to be solved by the inivention
The present invention is in order to solve the above-mentioned technical problem to complete, and its purpose is to provide a kind of chromatographic data processing sides
Method and device, the chromatographic data processing method are based on chromatographic data as described above three-dimensional, without user troublesome sentence
Disconnected and parameter input or setting, it will be able to estimate baseline appropriate relative to chromatography waveform.
In addition it is a further object of the present invention to provide a kind of chromatographic data processing method and device, chromatographic data processing
Method can respectively in mass spectrum that wavelength chromatography or each mass-to-charge ratio that each wavelength obtains obtain (extraction chromatography of ions figure),
Automatically estimate baseline appropriate.
Scheme for solving above-mentioned technical problem
In order to solve the above-mentioned technical problem the chromatographic data processing method of the present invention completed is to three-dimensional chromatographic data
The chromatographic data processing method handled, the three-dimensional chromatographic data are when collecting, having from measurement object i.e. sample
Countershaft, signal strength axis and the 3rd parameter axis, which is characterized in that have：
(a) spectrum peak obtaining step, obtains and be to be detected in chromatography that three-dimensional chromatographic data generates based on process object
Peak is corresponding, indicates the spectrum of the relationship of the 3rd parameter value and signal strength values；
(b) baseline chromatography waveform estimates step, and multi-C vector is projected in and is obtained in the spectrum peak obtaining step
On the orthogonal direction of vector direction when spectrum is expressed with vector, and the size of thus obtained projection vector is found out as the time
Sequence signal estimates the waveform shape for the baseline chromatography for indicating the baseline in chromatography, the multidimensional based on the time series signal
Vector is the spectrum expressed with vector respectively according to the three-dimensional chromatographic data in each time of measuring point.
In addition, the chromatography data system of the present invention is the dress for the chromatographic data processing method for implementing aforementioned present invention
It sets, to from measurement object, that is, sample collection, three-dimensional chromatography number with time shaft, signal strength axis and third parameter axis
According in the chromatography data system handled, which is characterized in that have：
(a) spectrum peak acquisition unit obtains detected in the chromatography based on the i.e. three-dimensional chromatographic data generation of process object respectively
Each peak it is corresponding, indicate the spectrum of the relationship of the 3rd parameter value and signal strength values；
(b) baseline chromatography waveform presumption unit, multi-C vector is projected in the spectrum that is obtained with the spectrum peak acquisition unit with
On the orthogonal direction of vector direction when vector expression, and the size of thus obtained projection vector is found out as time series
Signal estimates the waveform shape for the baseline chromatography for indicating the baseline in chromatography, the multi-C vector based on the time series signal
It is the spectrum expressed with vector respectively according to the three-dimensional chromatographic data in each time of measuring point.
Relative to the sample for including the various compounds detached in the direction of time by chromatographic chromatographic column, passing through
The multi-channel type detectors of PDA detectors etc. repeats to obtain absorption spectrum or fluorescence spectrum etc., thus collects three-dimensional chromatography number
In the case of, above-mentioned " the 3rd parameter axis " refers to wavelength axis.
In addition, relative to the sample for including the various compounds detached in the direction of time by chromatographic chromatographic column,
In the case of repeating to collect three-dimensional chromatographic data by obtaining mass spectrum by mass spectrograph, above-mentioned " the 3rd parameter axis " refers to matter lotus
Than m/z axis.
And then in addition, collect the feelings of three-dimensional chromatographic data in the comprehensive two dimensional gas chromatography instrument by full two dimension GC, full two dimension LC etc.
Under condition, above-mentioned " the 3rd parameter axis " refers to time (retention time).In this case, in three axis two be time shaft, one of them
The time scale of time shaft is big, another time shaft indicates thinner time scale.
In addition, " three-dimensional chromatographic data " said here can also be by Flow Injection Analysis (FIA=Flow
Injection Analysis) method to sample via chromatographic chromatographic column instead of carrying out ingredient separation, relative to non-ingredient
The data that the multi-channel type detector or mass spectrometric sample for detaching and being fed to PDA detectors etc. obtain.
In the chromatographic data processing method of the present invention and device, the pass of the 3rd parameter value and signal strength values will be indicated
The spectrum of system is for example handled using absorption spectrum or mass spectrum as with the multi-C vector of vector expression.For example, if being to absorb light
Spectrum, then the set of the absorbance of discrete each wavelength is absorption spectrum, so using absorption spectrum as (a (λ 1), a (λ 2), a (λ
3) ... ..., a (λ n)) it indicates, the multi-C vector definition as ingredient by a (λ m) can be defined.Here, a (λ m) is wavelength m (λ
=1~n) absorbance.In addition, chromatography can also be handled similarly as multi-C vector.
The i.e. above-mentioned three-dimensional chromatographic data of process object, can add up to two following vectorial direct products and be modeled
Change, one of vector be drawn in the plane of two axis including time shaft and signal strength axis, by each compound
Chromatographic grade vector expressed, another vector is strong with signal including the 3rd parameter axis (such as wavelength axis or mass-to-charge ratio axis)
Spend it is being drawn in the plane of two axis of axis, the spectrum of each time of measuring point expressed with vector.If currently, sample institute
It it is two kinds containing compound, then the three-dimensional chromatographic data D obtained relative to the sample is according to following equation modelingization.
D=C1·S1 T+C2·S2 T
Here, C1And C2It is the vector expression of the chromatographic signal of the compound relative to the 1st and the 2nd, S respectively1、S2
Be respectively the 1st and the 2nd time of measuring point in wave spectrum signal vector expression.
If the wave spectrum S of the 1st compound1It is known that can then find out and wave spectrum S1Orthogonal vectorial R1, lead to
It crosses vector R1Be multiplied by the three-dimensional chromatographic data D indicated by above-mentioned equation, then with the 1st compound phase on the right of above-mentioned equation
The item of pass disappears, the chromatographic signal C of the 2nd compound2Multiplication by constants (wave spectrum S2Vector with vector R1Inner product) and obtain
α C2.The α C2It is the chromatographic signal C for indicating the 2nd compound2Waveform shape vector.Even if changing contained in sample
The quantity for closing object is 3 kinds or more, this is also identical.That is, it can be said that contained compound is feelings of more than two kinds in the sample
Under condition, as long as the wave spectrum of wherein a kind compound is unknown and the wave spectrum of every other compound is known, then can
Enough find out a kind of waveform shape of the chromatographic signal of unknown compound.
Also, this refers to occurring on relative to chromatography if baseline is considered as a kind of chromatography of unknown compound
When known to the wave spectrum of all peaks (peak corresponding with all compounds), the waveform shape of unknown baseline is found out.At this
In the chromatographic data processing method and device of invention, the waveform shape of baseline is estimated according to such principle.
That is, in the chromatographic data processing method of the present invention, in spectrum peak obtaining step, based on process object i.e. three
Peak is detected in the chromatography that dimension chromatographic data generates, obtains spectrum corresponding with the peak detected respectively.Relative to a peak, that is, phase
For a kind of compound, a spectrum only need to be obtained.The spectrum of all compounds other than unknown baseline as a result,
Become known.Then, in the baseline chromatography waveform presumption step for continuing to implement, respectively for according to each of three-dimensional chromatographic data
The vector of the spectrum of time of measuring point keeps it orthogonal in the vector direction of the spectrum correspondingly obtained with peak as described above
It is projected on direction, finds out signal value i.e. time series signal of the size of projection vector as each time of measuring point.It asks as a result,
Go out and above-mentioned α C2Corresponding signal indicates the signal of the waveform shape of baseline.
In addition, the peak detected in chromatography is multiple spectrum corresponding with the peak be also multiple in the case of, example
Such as, as long as finding out the time of the size based on the projection vector on orthogonal to that direction according to vector corresponding with the spectrum
Sequence signal, and carry out total to multiple time series signal in each time of measuring point and find out a time series signal
?.However, when carrying out such total, need the benchmark of each signal magnitude that must be consistent, thereby it is preferred that for example
After a pair signal strength for spectrum corresponding with each peak is normalized, implement the place of baseline chromatography waveform presumption step
Reason.
Even if intensity value of baseline itself is unknown, if the waveform shape of baseline can be estimated as described above, it is based on
The presumption is as a result, it is possible to judge in the multiple baseline candidates for example estimated according to previous various baselines presumption method
Which is more appropriate.
In addition, preferred 1st scheme of chromatographic data processing method of the present invention, which is characterized in that also have baseline spectrum
Estimate step, a part to the chromatography that each of generates the 3rd parameter value according to the three-dimensional chromatographic data or it is each this one
Part carries out the fitting for estimating the baseline chromatography waveform obtained in step in the baseline chromatography waveform, thus finds out each 3rd
The signal strength values of the baseline of parameter value indicate the relationship of the 3rd parameter value and signal strength values in baseline based on this presumption
Baseline spectrum.
If finding out baseline spectrum according to above-mentioned 1st scheme, the constant α of each 3rd parameter value, therefore energy can be obtained
Enough find out the baseline in the chromatography of each 3rd parameter value.It as a result, also can be to for example each wavelength of the 3rd parameter value or each matter
Lotus is than making the peak chromatography for eliminating baseline and only retaining peak.
In addition, in the chromatographic data processing method of the present invention, it preferably, can also be in the spectrum peak obtaining step
In, by using filter, estimate in chromatography that there are the time ranges at peak, and obtain light corresponding with peak within this time range
Spectrum, the filter exports zero when input changes over time slow signal waveform, and is changed over time rapidly in input
Non-zero is exported when signal waveform.
Here, above-mentioned filter is such as can use Savitzky-Golay filters.
In general, the time change of the signal in baseline than peak-to-peak signal time change more slowly.Therefore, by making
With the filter of above-mentioned characteristic, quite accurately and the peak from compound can be quickly detected.It is of course also possible to by this
It is combined use using the method and other blob detection methods of filter.
In addition, as long as above-mentioned filter has filter parameter determining as follows：In the chromatography of offer,
Relative to the signal that the time range there is only baseline is either estimated as there is only baseline output, with relative to there are peak or
It is estimated as that there are the ratio between the output of signal of time range at peak maximums.
Invention effect
Chromatographic data processing method according to the present invention and device, such as the cumbersome judgement and defeated that is carried out without user
Enter or setup parameter, and the waveform for the baseline being overlapped in the chromatography generated according to three-dimensional chromatographic data can be estimated with high precision
Shape, the three-dimensional chromatographic data are multi-channel type detector by having used PDA detectors etc. or mass spectrograph as detector
What chromatograph was collected.The presumption of the waveform shape based on baseline as a result, it is possible to accurately judge for example according to each in the past as a result,
Which of multiple baseline candidates of baseline presumption method presumption of kind various kinds are more appropriate, and can carry out high-precision base
Line corrects.
In addition, the 1st scheme of chromatographic data processing method according to the present invention, can estimate each wavelength, each matter lotus
Than etc. chromatography in baseline.Thereby, it is possible to precisely make removal baseline to each wavelength or mass-to-charge ratio and there is only
The peak chromatography at peak, for example, can be carried out based on the accurate area value at peak corresponding with each compound high-precision quantitative.
Description of the drawings
Fig. 1 is an embodiment of the LC devices for the data processing equipment for having the chromatographic data processing method for implementing the present invention
Schematic configuration diagram.
Fig. 2 (a) is to indicate by the concept map of the LC three-dimensional chromatographic datas analyzed, and Fig. 2 (b) is an example of wavelength chromatography
Figure.
Fig. 3 is the general flowchart of the peak waveform processing entirety in the LC devices of the present embodiment.
Fig. 4 is the flow of the specific step of the spectrum set { Sn } in the LC devices indicated for obtaining the present embodiment
Figure.
Fig. 5 is the flow chart of the baseline chromatography waveform presumption processing of the spectrum peak in the LC devices based on the present embodiment.
Fig. 6 is the chromatography of an example for the separating resulting for indicating baseline waveform and spike shape.
Fig. 7 is the wave spectrum of an example for the separating resulting for indicating baseline waveform and spike shape.
Fig. 8 is to indicate according to previous peak waveform processing method, the baseline estimated relative to chromatography waveform and peak P's
The figure of an example in area value computing object region.
Specific implementation mode
Hereinafter, being illustrated to the chromatographic data processing method of the present invention and an embodiment of device with reference to attached drawing.
Fig. 1 is an embodiment of the LC devices for the data processing equipment for having the chromatographic data processing method for implementing the present invention
Schematic configuration diagram.
The LC devices of the present embodiment have the portions LC 1, data processing division 2, input unit 3 and display unit 4.In the portions LC 1, send
Liquid pump 12 aspirates mobile phase from mobile phase container 11 and supplies mobile phase to syringe 13 with constant flow rate.Syringe 13 is providing
Opportunity test liquid is injected into mobile phase.The test liquid injected is pressed into mobile phase and is fed to chromatographic column 14,
Each compound during by chromatographic column 14 in the test liquid is detached and is eluted in the direction of time.It is connected to chromatographic column 14
The PDA detectors 15 of outlet, relative to as time goes by successively imported eluent duplicate measurements in defined wavelength model
Absorbance distribution (absorption spectrum) in enclosing.The signal obtained according to the measurement is converted in analog-digital converter (ADC) 16
It is input to data processing division 2 at numerical data, and as three-dimensional chromatographic data.
The data processing division 2 for receiving above-mentioned data has such as the following functional block：Chromatographic data storage part 21 accommodates three-dimensional
Chromatographic data；Baseline presumption unit 22 estimates the baseline of chromatography based on three-dimensional chromatographic data；Peak chromatography calculating part 23, uses presumption
Baseline find out removal baseline after peak chromatography；Qualitative processing unit 24 carries out qualitative processing based on the peak chromatography found out and identifies
Compound；Quantitative Treatment portion 25 carries out quantitative calculating based on peak chromatography.The input unit 3 for being connected to data processing division 2 is, for example, to use
In the various parameters etc. needed for user input data processing, display unit 4 is used for the chart of customer prompts chromatography etc. or qualitative/fixed
Measure result etc..
In addition, the entity of usually data processing division 2 is the work station of personal computer or higher function, can be configured to logical
Crossing makes to be installed on that computer the exclusive data processing software work of these computers in advance, above-mentioned each to implement
Functional block.
In the LC analytical equipments of the present embodiment, by executing LC analyses to a sample in the portions LC 1, collect from sample
Injection length point is the three-dimensional chromatography number measured in sart point in time to the time range for measuring end time point, as shown in Figure 2 a
According to, and it is stored in chromatographic data storage part 21 as a data file.If user (hereinafter referred to as " operator ") is defeated
Enter 3 middle finger of portion be set for for process object data file and instruction start execute peak waveform processing, then baseline presumption unit 22 and
Peak chromatography calculating part 23 executes characteristic processing as described below.
Fig. 3 is the general flowchart of peak waveform processing entirety.
Here, absorption spectrum or chromatography are handled as with the multi-C vector of vector expression.For example, if being to absorb
Absorption spectrum is expressed as (a (λ 1), a by spectrum then because the set of the absorbance of discrete each wavelength is absorption spectrum
(λ 2), a (λ 3) ... ..., a (λ n)), the multi-C vector using a (λ m) as ingredient can be defined.Here, a (λ m) is wavelength m (λ
=1~n) absorbance.
Process object i.e. with wavelength, the time, signal strength these three dimensions three-dimensional chromatographic data D, can will with to
The direct product for measuring the chromatographic signal of expression is added up to with the direct product of wave spectrum (absorption spectrum) signal of vector expression, to
Modelingization, the relationship of the time and signal strength values of each compound in the chromatographic signal representing sample, the wavelength light
Spectrum (absorption spectrum) signal indicates the wavelength of each measurement time and the relationship of signal strength values.That is, three-dimensional chromatographic data D can
With following (1) equation modelingization.
D=C1.S1 T+C2.S2 T+…+Cm.Sn T…(1)
C1~CmIt indicates to express the vector of the 1st to the compound of m chromatographic signal, S1~SnIt indicates from the 1 to the n-th
Each measurement time (time of measuring point) in wave spectrum signal vector expression.
Here, defining precondition of the following three points as presumption baseline.In addition, these conditions are in LC analyses etc.
It is appropriate.
[condition A] is in the process object i.e. end (starting point of i.e. all time of measuring ranges of at least one party of chromatographic data
Or terminal) in, baseline is main signal component, in addition to this not significant signal component, i.e., without coming from compound
Signal component.
Compared with the Fluctuation of analytical signal at the peak from compound very slowly, i.e., time change is small for the variation of [condition B] baseline.
The wave spectrum of [condition C] baseline is different from the wave spectrum of any compound.
Under the conditions of above three, baseline presumption unit 22 and peak chromatography calculating part 23 estimate baseline according to the following steps,
And calculate the peak chromatography for eliminating the baseline.
First, the three-dimensional chromatographic data that baseline presumption unit 22 is analyzed from the reading of chromatographic data storage part 21 LC is (following
Referred to as " observation data ") (step S1), based on the wave spectrum found out from the observation data, presumption indicates the baseline in chromatography
The waveform shape (step S2) of the baseline chromatography of time change.In addition, specific herein is only waveform shape, each wavelength it is strong
Angle value itself is unknown.
Then, peak chromatography calculating part 23 estimates the base of each wavelength based on the baseline chromatography waveform estimated in step s 2
The intensity value of line chromatography, the i.e. wave spectrum (hereinafter referred to as " baseline spectrum ") (step S3) of baseline.Then, according to baseline chromatography
Vector with baseline spectrum vector direct product, the background signal (step S4) in the chromatography of each wavelength is found out, to each wave
It is long by subtracting background signal from observation data, calculating eliminates baseline and the peak chromatography (step S5) there is only spike shape.
It is described in detail to being managed everywhere in above-mentioned steps S2~S5.Here, to simplify the explanation, to only being wrapped in sample
Example containing the 1st and the 2nd two kind of compound accounts for.In this case, observation data D is indicated by equation (2).
D=C1.S1 T+C2.S2 T…(2)
If it is now assumed that the wave spectrum S of the 1st compound1For it is known that can then find out and wave spectrum S1Vector side
To orthogonal vectorial R1.If by vector R1The 2nd chemical combination can be obtained then as shown in equation (3) by being multiplied by observation data D
The chromatographic signal C of object2Vectorial multiplication by constants (wave spectrum S2Vector with vector R1Inner product) α C2。
DR=C1·S1 T·R1+C2·S2 T·R2=0+C2·(S2 T·R2)=α C2…(3)
The α C2Indicate the chromatographic signal C of the 2nd compound2Waveform shape.
Even if the quantity for the compound that sample is included is 3 kinds or more, as long as the wave spectrum of one of which compound is not
Know and the wave spectrum of other all compounds is known, so that it may to say being identical.And, it means that if baseline is regarded
For a kind of chromatography of unknown compound, if it is known that the wave at all peaks (peak corresponding with all compounds) occurred in chromatography
Long spectrum then finds out the shape of unknown baseline.Here, estimating baseline according to such principle.
Fig. 5 is the flow chart for the detailed step for indicating the baseline chromatography waveform presumption processing in above-mentioned steps S2.
Baseline presumption unit 22 carries out blob detection to the chromatography generated based on observation data, extracts all peaks.Then, from
The wave spectrum of the time of measuring point of the summit at each peak in extracting data chromatography is observed, and obtains the spectra collection including it
Close { Sn(step S10).
At this point, in order to detect peak corresponding with each compound of the influence for the wave spectrum for eliminating baseline, utilization is above-mentioned
Condition B.That is, the time fluctuation due to baseline is slow, so baseline is in local fully approximating polynomial.On the other hand, it comes from
The Fluctuation of analytical signal at the peak of the compound occurred in chromatography is very rapid compared with the variation of baseline, thus the peak there are the case where
Under, it will produce systematic approximate error when wanting approximating polynomial.Because the systematic approximate error is there are peaks
Equally occur in multiple wavelength, so the data of extraction system error become chromatographic peak do not influenced by baseline and pure
Corresponding wave spectrum.
Therefore, herein in order to detect peak, following filter is utilized：For slowly becoming as being present in baseline chromatography
Change or only have the signal output zero of the simple changes such as linear or exponential function, and the system for exporting non-zero for peak-to-peak signal is missed
Difference.But in the wavelength there are peak, need for all wavelength all generation system errors in the same manner.That is, it needs to not depend on
The ratio of baseline and peak height in chromatography, and obtain the height at the peak being multiplied by fixed number corresponding with the shape of peak chromatography
Value.This means that it may be said that the filter is linear filter.As such filter, for example, Savitzky- can be used
Golay filters etc..
Fig. 4 is indicated for obtaining the spectrum set { S in above-mentioned steps S10nSpecific step an example flow
Figure.
First, it is based on above-mentioned condition A, the baseline light that the wave spectrum in the end of time of measuring range is determined as assuming
It composes (step S20)." end " includes that the starting point (measuring sart point in time) of time of measuring range and terminal (measure the end time
Point) this 2 points, it is excellent in order to improve the precision of baseline presumption although the wave spectrum in the end of any one can be used
Implement subsequent processing respectively when being selected in the wave spectrum of selection starting point and when the wave spectrum of selection terminal, and takes presumption base respectively
Line it is average etc..
Then, Quadratic function is carried out to the chromatographic signal of each wavelength using Savitzky-Golay filters, with
Find out remnants (systematic error) signal (step S21).Then, it cuts out each wavelength and is exported there are residue signal i.e. filter and be
The time range of non-zero, and find out the wave spectrum (step S22) in the time range.It obtains corresponding to institute in chromatography as a result,
There is the wave spectrum at peak.However, in obtained wave spectrum, if there is the wavelength essentially identical with baseline spectrum is assumed
In the case of spectrum, then discarded (step S23).This is because such spectrum may lead to operation mistake.
Spectrum set { S is made by collecting finally obtained wave spectrum as described aboven(step S24).
Continue to illustrate back to Fig. 5.If obtaining spectrum set { S in step 10n, then for the set { Sn}
In include each wave spectrum into exercise L2 norms become 1 normalization (step S11).Then, from the spectra collection after normalization
Close { Sn' in, select the ingredient orthogonal relative to the vector direction of baseline spectrum (size of the vector on orthogonal direction) maximum
Wave spectrum Smax(step S12), judges whether the orthogonal component is less than predetermined specified value (step S13).In maximum
In the case that the value of orthogonal component is less than specified value, if judging, there is no the peak that should be detached, to proceed to S17 from step S13.
On the other hand, the value of maximum orthogonality ingredient then proceeds to S14 more than specified value from step S13, with selected wave
Long spectrum SmaxThe orthogonal mode of vector direction, respectively to the wave spectrum of each time of measuring point based on observation data to
Amount is projected (step S14).Specifically, using the vector of the wave spectrum in some time of measuring point as when A, by it
It is updated to A- (ASmax)·Smax.In turn, to the vector of all wavelengths spectrum contained by spectrum set { Sn ' }, also with it is above-mentioned
Wave spectrum SmaxThe orthogonal mode of vector direction projected (step S15).Selected wave spectrum S as a result,maxVector
Size becomes zero, therefore from spectrum set { Sn' be removed.Hereafter, judge spectrum set { Sn' in whether remaining wave spectrum
(step S16) returns to S12 from step S16, repeats the processing of step S12~S16 if remaining.
In the case of being judged as NO in step s 16, or in the case of being judged as NO in step 12, existing will be only surplus
The observation data of lower orthogonal component are multiplied by chromatographic signal C obtained from various coefficients2.That is, being various there are α values
α C2.At this point, the constant α may be negative polarity.Therefore, in the chromatographic signal α C that will be found out2Constant α and positive polarity pair
On the basis of neat, the signal value of all chromatographic signals is added up in each time of measuring point, thus calculates and indicates baseline
The signal (step S17) of chromatography waveform.Baseline chromatography waveform can be estimated in this way.
Then, the step of being estimated to the baseline chromatography in above-mentioned steps S3 illustrates.
According to above-mentioned condition A, since the signal of the end of time of measuring range is only background signal, so in order to match it
Height is signal level, as long as being fitted the baseline chromatography waveform of above-mentioned presumption.However, for example, due to noise etc. influence,
There is a situation where to use the signal in the end of time of measuring range may not be appropriate as the benchmark of fitting.Therefore, with according to warp
It tests determining division number appropriate to be split entire time of measuring range and find out multiple local time's ranges, to each office
Portion's time range attempts fitting as described above, then, the most good local time's range of fit solution is regarded as and is only deposited
In the time range of baseline ingredient.
Here, being fitted the whether good judgement of situation in accordance with the following steps.
First, in each wavelength and in each local time's range, the fitting of baseline is carried out to chromatography based on observation data
And calculate residue signal.Using the L1 norms of the residual signal as the fractional value for indicating the error degree in being fitted.That is, fitting is got over
Well, score value is smaller.
However, when baseline becomes larger, also there is bigger tendency in the estimation error of chromatography therewith.Therefore, in order to
The influence is corrected, peak-peak (Peak-to-peak) value of the input signal within the scope of local time is preferably found out, with the value
Square root divided by fractional value.In addition, in close i.e. local time range of the score value difference within prescribed limit of fractional value
In the case of multiple, preferentially to handle the local time close to the end for being estimated as the time of measuring range there is only baseline
The mode of range, will be 6 times maximum in 1 times in local time's range close to the end, the part-time range far from end
Weight be multiplied by fractional value.Then, the obtained fractional value of each wavelength is added up in each local time's range, and
And final score value of the calculating relative to local time's range.It, can also be for example based on Heuristics or dress when this adds up to
The SN set than measurement result etc. be weighted.
If finding out the fractional value of each local time's range respectively in this way, the minimum wherein provided is selected
Local time's range of fractional value is as baseline section.Then, according to the baseline in the baseline section, each wave of baseline is determined
Long intensity, i.e. baseline spectrum.
In addition, the evaluation criteria of residue signal is not limited to L1 norms, L2 norms or maximum-minimum value etc. can also be used.
In addition, attempted except fitting except through being divided to each local time's range, it can also be by using moving window
Or weighting moving window is attempted to be fitted to each window.
As described above, finding out baseline chromatography waveform and baseline spectrum.As previously mentioned, these direct products become each of presumption
The background signal of wavelength.Also, the baseline in the wavelength is subtracted from the chromatography of each wavelength obtained based on observation data, it can
Find out the peak chromatography that the i.e. removal baseline after baseline correction influences.
Fig. 6 is the separation knot for indicating background signal and peak-to-peak signal when using the chromatographic data processing method of the present embodiment
The chromatography of an example of fruit, Fig. 7 are the spectrum of an example for indicating identical separation result.These are to intentionally by the base of exponential function
Line is respectively added to the data in the chromatography and wave spectrum obtained in actually measuring, by applying above-mentioned peak waveform processing
Attempt the result of separation background signal and peak-to-peak signal.Fig. 6 (b) is the grand of time range and the peak existing for peak in Fig. 6 (a)
Play the enlarged drawing of part.According to the Fig. 6 (b), the time range existing for peak can estimate curvilinear baseline well, thus
Understand peak-to-peak signal by well from baseline separation.In addition, as can be seen from Figure 7, in wave spectrum peak-to-peak signal and background signal also by
It detaches well.
In addition, in the processing of above description, it, can also although the baseline presumption result using chromatography finds out peak chromatography
As former state using processing of the baseline presumption result without being removed baseline, and by the presumption result for select in various ways or
The baseline that algorithm is found out.
For example, as described in the example of Fig. 8, previous data processing equipment is automatically found out equipped with waveform processing function
Utilize the curve baseline etc. of straight line basis or Gaussian function etc..Therefore, if obtaining baseline by data processing as described above
Presumption selects most as a result, result then can also be estimated with reference to the baseline in the baseline found out by existing multiple waveform processings
Baseline appropriate.
In addition, according to the data processing method of the present embodiment, the pure wave spectrum at the peak in each chromatography is found out first, then
Baseline chromatography waveform, baseline spectrum are found out successively.Accordingly it is also possible to the rank of the pure wave spectrum at peak on finding out each chromatography
Section, identifies compound according to the wavelength etc. for appearing in the absorption peak in the wave spectrum.
In addition, chromatographic data processing method or LC analytical equipments in the above-described embodiments is an example of the present invention, even if
Carry out in the range of the purport of the present invention it is appropriate deformation, addition, modification, also certainly by the claim institute of the application patent
Including.
For example, in the present invention, obtaining the detector that process object is the chromatography of three-dimensional chromatographic data, can not be as above
The multi-channel type detector of the PDA detectors etc. can also be the UV, visible light light splitting that can carry out high speed length scanning
Photometer, infrared spectrophotometer, near infrared spectrometer, sepectrophotofluorometer etc..In addition it is also possible to be as described above
Ground is using mass spectrograph as the liquid chromatography mass instrument or gas chromatography mass spectrometer of detector.
In addition, being not and to flow note passing through using the detections such as PDA detectors by the analysis of chromatographic chromatographic column
The data obtained in the case of the sample for penetrating the importing of analysis (FIA) method are also with these three dimensions of time, wavelength and absorbance
The three-dimensional data of degree is substantially identical as the three-dimensional chromatographic data collected by liquid chromatograph.It is therefore apparent that the present invention
It can be applied to the device handled such data.
Reference sign
1 portions LC
11 mobile phase containers
12 liquid-feeding pumps
13 syringes
14 chromatographic columns
15 PDA detectors
2 data processing divisions
21 chromatographic data storage parts
22 baseline presumption units
23 peak chromatography calculating parts
24 qualitative processing units
25 quantitative Treatment portions
3 input units
4 display units
Claims (6)
1. a kind of chromatographic data processing method, to the sample collection from measurement object, have time shaft, signal strength axis and
The three-dimensional chromatographic data of 3rd parameter axis is handled, which is characterized in that is had：
(a) spectrum peak obtaining step is obtained detected in the chromatography generated based on the i.e. three-dimensional chromatographic data of process object respectively
Each peak it is corresponding, indicate the spectrum of the relationship of the 3rd parameter value and signal strength values；
(b) baseline chromatography waveform estimates step, and multi-C vector is projected in and the spectrum that is obtained in the spectrum peak obtaining step
On the orthogonal direction of vector direction when being expressed with vector, and the size of thus obtained projection vector is found out as time series
Signal estimates the waveform shape for the baseline chromatography for indicating the baseline in chromatography, the multi-C vector based on the time series signal
It is the spectrum expressed with vector respectively according to the three-dimensional chromatographic data in each time of measuring point.
2. chromatographic data processing method as described in claim 1, which is characterized in that also there is baseline spectrum to estimate step, it is right
According to a part for the chromatography of the 3rd parameter value of each of the three-dimensional chromatographic data generation or each part, exist
The fitting of the baseline chromatography waveform obtained in the baseline chromatography waveform presumption step, thus finds out the base of each 3rd parameter value
The signal strength values of line indicate the baseline spectrum of the relationship of the 3rd parameter value and signal strength values in baseline based on this presumption.
3. chromatographic data processing method as described in claim 1, which is characterized in that in the spectrum peak obtaining step, lead to
It crosses and uses filter, there are the time ranges at peak in presumption chromatography, and obtain spectrum corresponding with peak, institute within this time range
It states filter and exports zero when input changes over time slow signal waveform, and rapid signal wave is changed over time in input
Non-zero is exported when shape.
4. chromatographic data processing method as claimed in claim 3, which is characterized in that the filter is Savitzky-Golay
Filter.
5. chromatographic data processing method as claimed in claim 3, which is characterized in that the filter has as follows really
Fixed filter parameter：In the chromatography of offer, relative to there is only baseline or being estimated as time range there is only baseline
Signal output, with relative to there are peak or being estimated as that there are the ratio between the output of signal of time range at peak is maximum.
6. a kind of chromatography data system, to the sample collection from measurement object, have time shaft, signal strength axis and
The three-dimensional chromatographic data of 3rd parameter axis is handled, which is characterized in that is had：
(a) spectrum peak acquisition unit, obtains and be to detect in chromatography that three-dimensional chromatographic data generates based on process object respectively
Each peak is corresponding, indicates the spectrum of the relationship of the 3rd parameter value and signal strength values；
(b) multi-C vector is projected in the spectrum obtained with the spectrum peak acquisition unit with vector by baseline chromatography waveform presumption unit
On the orthogonal direction of vector direction when expression, and find out the size of thus obtained projection vector as time series signal,
The waveform shape for the baseline chromatography for indicating the baseline in chromatography is estimated based on the time series signal, the multi-C vector is difference
The chromatography according to the three-dimensional chromatographic data in each time of measuring point is expressed with vector.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2016/050270 WO2017119086A1 (en) | 2016-01-06 | 2016-01-06 | Chromatogram data processing method and device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108780074A true CN108780074A (en) | 2018-11-09 |
| CN108780074B CN108780074B (en) | 2021-03-02 |
Family
ID=59273385
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680083134.1A Active CN108780074B (en) | 2016-01-06 | 2016-01-06 | Chromatogram data processing method and chromatogram data processing device |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US10725000B2 (en) |
| JP (1) | JP6583433B2 (en) |
| CN (1) | CN108780074B (en) |
| WO (1) | WO2017119086A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7018297B2 (en) * | 2017-11-16 | 2022-02-10 | 日本電子株式会社 | Spectrum analyzer and method |
| JP7018321B2 (en) | 2018-01-12 | 2022-02-10 | 日本電子株式会社 | Spectrum processing equipment and method |
| US11169127B2 (en) * | 2019-06-10 | 2021-11-09 | Korea Resources Corporation | Method for measuring the concentration of aliphatic hydroxy oxime and neodecanoic acid by gas chromatography |
| EP4160204A4 (en) | 2020-05-28 | 2024-07-03 | Shimadzu Corp | Peak tracking device, peak tracking method, and peak tracking program |
| CN113671234B (en) * | 2021-08-24 | 2023-09-12 | 华北电力大学（保定） | Short air gap streamer discharge path observation system and prediction method |
| CN115856185B (en) * | 2023-02-28 | 2023-06-13 | 杭州泽天春来科技有限公司 | Processing method and system of analyzer and readable storage medium |
| CN117785818B (en) * | 2024-02-26 | 2024-05-10 | 山东惠分仪器有限公司 | Gas chromatograph data optimized storage method and system |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1070482A (en) * | 1991-06-30 | 1993-03-31 | 株式会社岛津制作所 | Be used for chromatographic absorbance analyzer and data processing method |
| JPH08101064A (en) * | 1994-09-30 | 1996-04-16 | Jasco Corp | Method and apparatus for estimating and producing base line |
| US5969228A (en) * | 1996-04-12 | 1999-10-19 | Waters Investments Limited | Method and devices for chromatographic pattern analysis employing chromatographic variability characterization |
| WO2015056311A1 (en) * | 2013-10-16 | 2015-04-23 | 株式会社島津製作所 | Chromatogram data processing device |
| CN105026926A (en) * | 2013-03-04 | 2015-11-04 | 株式会社岛津制作所 | Chromatogram data processing device and processing method |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MY107650A (en) | 1990-10-12 | 1996-05-30 | Exxon Res & Engineering Company | Method of estimating property and / or composition data of a test sample |
| WO2005079263A2 (en) | 2004-02-13 | 2005-09-01 | Waters Investments Limited | Apparatus and method for identifying peaks in liquid chromatography/mass spectrometry data and for forming spectra and chromatograms |
| JP5211753B2 (en) | 2008-02-27 | 2013-06-12 | 株式会社島津製作所 | Chromatographic data processor |
| US20140179020A1 (en) * | 2012-12-20 | 2014-06-26 | David A. Wright | Methods and Apparatus for Identifying Ion Species Formed during Gas-Phase Reactions |
| JP6132073B2 (en) * | 2014-06-24 | 2017-05-24 | 株式会社島津製作所 | Comprehensive 2D chromatograph data processor |
-
2016
- 2016-01-06 JP JP2017559979A patent/JP6583433B2/en active Active
- 2016-01-06 WO PCT/JP2016/050270 patent/WO2017119086A1/en active Application Filing
- 2016-01-06 US US16/068,197 patent/US10725000B2/en active Active
- 2016-01-06 CN CN201680083134.1A patent/CN108780074B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1070482A (en) * | 1991-06-30 | 1993-03-31 | 株式会社岛津制作所 | Be used for chromatographic absorbance analyzer and data processing method |
| JPH08101064A (en) * | 1994-09-30 | 1996-04-16 | Jasco Corp | Method and apparatus for estimating and producing base line |
| US5969228A (en) * | 1996-04-12 | 1999-10-19 | Waters Investments Limited | Method and devices for chromatographic pattern analysis employing chromatographic variability characterization |
| CN105026926A (en) * | 2013-03-04 | 2015-11-04 | 株式会社岛津制作所 | Chromatogram data processing device and processing method |
| WO2015056311A1 (en) * | 2013-10-16 | 2015-04-23 | 株式会社島津製作所 | Chromatogram data processing device |
Also Published As
| Publication number | Publication date |
|---|---|
| US20190011408A1 (en) | 2019-01-10 |
| WO2017119086A1 (en) | 2017-07-13 |
| CN108780074B (en) | 2021-03-02 |
| JP6583433B2 (en) | 2019-10-02 |
| JPWO2017119086A1 (en) | 2018-11-01 |
| US10725000B2 (en) | 2020-07-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108780074A (en) | Chromatographic data processing method and chromatography data system | |
| US10121643B2 (en) | Chromatography/mass spectrometry data processing device | |
| EP2344874B1 (en) | Methods of automated spectral peak detection and quantification without user input | |
| CN103765207B (en) | Chromatography data system and processing method | |
| CN105637360B (en) | Peak value end-point detecting method and detection means in waveform | |
| JP6037040B2 (en) | Chromatogram data processor | |
| JP2005291715A (en) | Odor measuring device | |
| EP3540425B1 (en) | Data analyzer for chromatography mass spectrometry | |
| US10935526B2 (en) | Liquid chromatograph and method for correcting detector output value fluctuation of liquid chromatograph | |
| JPWO2015029254A1 (en) | Chromatograph data processing apparatus and method | |
| CN109073615B (en) | Data processing apparatus | |
| JP6245387B2 (en) | Three-dimensional spectral data processing apparatus and processing method | |
| JP5930066B2 (en) | Chromatograph data processing apparatus and data processing method | |
| US10481138B2 (en) | Chromatogram data processing device and processing method | |
| US10416133B2 (en) | Chromatographic data processing device, data processing method, and chromatographic analysis system | |
| JP7012989B2 (en) | Liquid chromatograph and detector output value fluctuation correction means for liquid chromatograph | |
| JP2016017941A (en) | Data processing device and data processing method for chromatograph, and chromatographic analysis system | |
| WO2018158801A1 (en) | Spectral data feature extraction device and method | |
| JP2023131244A (en) | Analysis method using spectrum measurement device | |
| JPS63317763A (en) | Optical detector |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |